Epoxidized hydroaromatic acetals

ABSTRACT

Epoxidized derivatives of reaction products of aldehydes of the general formula I:   with dialcohols having at least one epoxidizable C=C double bond. The products are useful for preparing epoxy resins.   D R A W I N G

United States Patent 1151 3,682,969 Batzer et al. 1 Aug. 8, 1972 [54]EPOXIDIZED HYDROAROMATIC Primary Examiner-Norma S. Mileston ACETALSAtlorneyHarry Goldsmith, Joseph G. Kolodny and [72] Inventors: HansBatzer, Arlesheim; Erwin Ni- Mano Monaco kles Liestal; Otto ErnstPfeffingen; Daniel Porret, Binninen, all of [57] ABSTRACT SwitzerlandEpoxidized derivatives of reaction products of al- [73] Assigneez CibaGeigy AG dehydes of the general formula I: 221 Filed: May 21,1970 K R D[211 App]. No.: 39,524

Related US. Application Data /Rs [62] Division of Ser. No. 828,472, July21, 1959,

Pat. No. 3,538,115. R1

R5 R0 [52] US. Cl. ..260/338, 260/2 EA, 260/2 N, with dialcohols havingat least one epoxidizable C:

260/231 A, 260/232, 260/3401, 260/3409 C double bond. The products areuseful for preparing 511 1111.01. ..C07d 17/00 epoxy resin, [58] Fieldof Search ..260/338 1 Claim, No Drawings EPOXIDIZED HYDROAROMATICACETALS CROSS-REFERENCE TO RELATED APPLICATIONS This application is adivision of our pending application Ser. No. 828,472, filed July 21,I959, now Pat. No. 3,538,l l5.

SUMMARY OF THE INVENTION The invention relates to reacting aldehydes ofthe general formula I, such as A -tetrahydrobenzaldehyde,6-methyl-tetrahydrobenzaldehyde,2,5-endomethylene-A"-tetrahydrobenzal-dehyde, 6-methyl-2,-endomethylene-A -tetrahydrobenzaldehyde, etc. with a dialcoholcontaining at least one epoxidizable C=C double bond, such as2-butene-l,4-diol, butadiene monoxide. glycerine monallyl ether, etc.and then epoxidizing the resulting acetal.

DESCRIPTION OF THE PREFERRED EMBODIMENTS This invention relates toepoxidized hydroaromatic acetals and to processes for the productionthereof.

According to the present invention there are provided epoxidizedhydroaromatic acetals containing at least two epoxide groups and beingepoxy derivatives of acetals obtained by reaction between (a) aldehydesof the general formula I:

wherein R,, R,, R R R,, R, R,, R, and R. when taken individuallyrepresent monovalent substituents, such as halogen atoms, alkoxy groupsor aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbonradicals, (e.g. lower alkyl radicals, i.e., containing one to fourcarbon atoms) or hydrogen atoms, or R and R, taken together represent adivalent substituent, such as a methylene group, and (b) compoundscontaining at least two alcoholic hydroxyl groups (i.e. dialcohols orpolyalcohols), one of the epoxide groups being in each cyclohexane ringderived from the above aldehyde.

According to a further aspect of the invention there is provided aprocess for the production of the said epoxidized acetals whichcomprises subjecting to treatment with an epoxidizing agent an acetalcontaining at least two epoxidizable C=C double bonds and obtainable byreaction of an aldehyde of general formula I and a compound containingat least two alcoholic hydroxyl groups.

The epoxidizing reaction may be effected by conventional methods,advantageously with the aid of organic per acids, such as peraceticacid, parbenzoic acid, peradipic acid or monoperphthalic acid.Epoxidization may also be effected by treatment with hypochlorous acid,HOCI being added to the double bond in a first stage of the reaction,and the epoxide group being fonned in a second stage by treatment withan agent which splits off HCl for example a strong alkali.

Particularly advantageous properties are possessed by the diepoxidecompounds of the general formula II:

wherein h RI, R10 R1! R31 R3, b R4, R5! v R6! R R R R R and R representwhen taken individually, monovalent substituents, such as halogen atomsof aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbonradicals, (and preferably lower alkyl radicals having one to four carbonatoms) or represent hydrogen atoms, or R, and R taken together or R, andR, taken together, represent a divalent substituent, such as a methylenegroup.

The diepoxide compounds of the type of general formula II which are mosteasily available are those of the formula:

(7H (III, III

in which R and R represent hydrogen atoms or lower alkyl radicals.

Such compounds may have the formulas:

wherein A represents a tetravalent aliphatic radical which contains atleast four carbon atoms and which for example where there are three orfour or more such groupings, are also of importance.

The diepoxide compounds of the type of general formula [V which are mosteasily obtainable are those of the formula in which R and R' stand forhydrogen atoms or lower alkyl radicals and A for a tetravalent saturatedaliphatic hydrocarbon radical which is unsubstituted or is substitutedby at the most two hydroxyl groups, which contains four to six carbonatoms and which comprises no carbon atom with more than a single freevalency, and no hydroxyl groups bonded to carbon atoms with such a freevalency.

A said diepoxide compound is that of the formula:

These epoxides are light, fusible resins which can be transformed withsuitable hardening agents, for example dicarboxylic acid anhydrides,into clear and light, hardened products with excellent industrialproperties.

A further class of compounds within the present invention are thetriepoxide compounds of the general formula VI:

60 tetrahydrobenzaldehyde,

in which R, R and R represent hydrogen atoms or lower alkyl radicals andA represents a hexavalent saturated aliphatic hydrocarbon radical whichcontains six carbon atoms and which does not comprise any carbon atomswith more than a single free valency.

These epoxides have similar properties to the epoxides of generalfonnula V.

The preferred diepoxide compounds of formulae II or W are obtained byepoxidization of hydroaromatic l0 acetals of the formulae:

Rs Rs R5 R5 in which the various symbols have the meanings assigned tothem above.

The acetals used in the process according to the invention as startingcompounds and having at least two epoxidizable C C double bonds may forexample be obtained by condensing 1 mol of an aldehyde of fonnula l with1 mol of a dialcohol or polyalcohol which in addition contains at leastone epoxidizable C C double bond.

Alternatively, two mols of an aldehyde of the formula l or of a mixtureof two or more such aldehydes may be condensed with one mol of apolyalcohol having at least four hydroxyl groups. Depending on whetherthere is initially employed a homogeneous aldehyde of the formula 1 ormixtures of such aldehydes, there are obtained acetals of symmetricalstructure or mixtures of acetals having a symmetrical structure withthose of an unsymmetrical structure.

The acetalization can be effected by methods known per se, such as forexample by heating an aldehyde of the formula I together with thedialcohol or polyalcohol in the presence of an acid catalyst, such asfor example hydrochloric acid or toluene-p-sulfonic acid.

The aldehydes of formula I are derivatives of tetrahydrobenzene.Examples are: A- tetrahydrobenzaldehyde, 6-methyl-A-tetrahydrobenzaldehyde, 4-methyl-A"'-tetrahydrobenzaldehyde,2,4,6-trimethyl-A tetrahydrobenzaldehyde, 2,5-cndomethylene-A6-methyl-2,5-endomethylene-A -tetrahydrobenzaldehyde and 4- chloro-A-tetrahydrobenzaldehyde.

Dialcohols and polyalcohols which contain at least one cpoxidizable C Cdouble bond, are, for example,

65 2-butene-l, 4-diol, glycerine monoallyl ether, bu-

tanetriol-(l,2,4-)-monoallyl ether andl,2-bis[hydroxymethyl]-cyclohex-3-ene or dialcohols of the generalformula IX:

wherein the symbols have the meanings assigned to them above, forexample, 1, I -bis[hydroxymethyl]- cyclohex-B-ene, l 1 -bis-[hydroxymethyl ]-6-methylcyclohex-B-ene, 1,] -bis-[ hydroxymethyl]-2,4,6- trimethyl-cyclohex-Ii-ene, l 1 -bis-[ hydroxymethyll-2,5-endomethylene'cyclohex-3-ene and l l-bis-[hydroxymethyll-4-chlorocyclohex-3-ene.

The dialcohols of general formula [X are themselves readily obtainableby reaction with formaldehyde, in alkali medium, of aldehydes of generalformula 1 in which the radical R, represents a hydrogen atom.

Polyalcohols having at least four hydroxyl groups.

are, for example, erythritol, xylitol, arabitol, sorbitol, mannitol,dulcitol, talitol, iditol, adonitol and pentaerythritol, heptites and2,2,6,6-tetramethylolcyclohexene-( 1 )-ol. In addition, thosepolyalcohols which also contain other functional groups, for exam plesugars, such as glucose, galactose, mannose, fructose, and cane sugar,saccharic acids, such as glucuronic acid, galacturonic acid, and mucicacid, may also be employed. Polymeric compounds with free hydroxylgroups, such as polysaccharides and more especially polyvinyl alcohol orpartially hydrolysed polyvinyl acetate may also be employed.

By initially using those polyhydroxyl compounds which comprise, insuitable configuration, 2.(n+2) hydroxyl groups (n whole number), it ispossible to react one mol of such a polyalcohol with (n+2) mols of anAldehyde of the general formula l to obtain unsaturated acetals which,after epoxidation, contain (n+2), i.e., at least three, epoxide groups,each situated in cyclohexane rings.

Furthermore, the acetals used as starting compounds in the process ofthe invention may, for example, be obtained by reacting 1 mol of analdehyde of the general formula I with l mol of an epoxide which inaddition has one epoxidizable C C double bond, or by reacting at leasttwo mols of an aldehyde of general formula l with one mole of a compoundcontaining at least two epoxide groups. In these processes the reactionproceeds by fission of the epoxide grouping or groupings, thus:

in which Z, 2,, Z Z and L, represent suitable sub stituents.

It is thus possible for example to react 2 mols of an aldehyde ofgeneral formula I with 1 mol of butadienes dioxide or dicyclopentadienedioxide, or with 1 mol of diepoxidized fatty acids unsaturated inseveral positions, such as linolsic acids, whereby unsaturated aldehydes of general formula Vlll are obtained.

By starting with epoxide compounds having (n+2) epoxide groups (n awhole number), it is of course also possible to obtain unsaturatedacetals by reaction of one mol of such polyepoxides with (n+2) mols ofan aldehyde of general formula I which acetals contain,

after epoxidization, (n+2) epoxide. groups in each cyclohexane ring.

The epoxidized acetals of the invention, depending on the polyhydroxylcompound from which they are derived may contain other functionalgroups. Thus the epoxidized aoetals may contain free hydroxy groups aswell as the acetalized hydroxyl groups of the polyalcohol, and by suchvariations in the compounds, the properties such as bonding strength orhydrophilic character, of the epoxide compounds according to theinvention can be modified within wide limits.

The epoxidized aoetals of the invention react with the conventionalhardeners of epoxide compounds. Consequently, by adding such hardeningagents, they can be cross-linked or cured in a manner analogous to otherpolyfunctional epoxide compounds and epoxide resins, respectively. Basiccompounds or acid compounds, the latter for preference, are suitablehardening agents.

The following are examples of suitable hardening agents: amines oramides, such as aliphatic and aromatic primary, secondary and tertiaryamines, for example monobutylamine, dibutylamine and tributylamine,p-phenylene diamine, bis-[p-aminophenyllmethane, ethylene diamine,N,N-diethyl ethylene diamine, diethylene triamine,tetra-[hydroxyethylldiethylene triamine, triethylene tetraminetetraethylene pentamine, trimethylamine, diethylamine, triethanolamine,Mannich bases,

piperidine, piperazine, guanidine and guanidine derivatives such asphenyl diguanidine, diphenyl guanidine, dicyandiamide,aniline-formaldehyde resins, urea-formaldehyde resins,melamine-formaldehyde resins, polymers of aminostyrenes, polyamides, forexample those from aliphatic polyamines and dimerized or trimerizedunsaturated fatty acids, isocyanates, isothiocyanates; polyhydricphenols, for example resorcinol, hydroquinone, bis-(4-hydroxyphenyl)-dimethyl methane, quinone, phenol-aldehyde resins, oilmodifiedphenol-aldehyde resins, reaction products of aluminum alcoholates orphenolates with tautomerically reacting compounds of the type ofacetoacetic ester, Friedel-Crafts catalysts, for example AlCl SbCl,,SnCh, FeCl ZnCI BF, and their complexes with organic compounds;phosphoric acid.

However, the preferred hardeners are polybasic carboxylic acids andtheir anhydrides, for example phthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride or endomethylene tetrahydrophthalicanhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride,hexachloroendomethylene tetrahydrophthalic anhydride or mixturesthereof; malcic or succinic anhydrides. Accelerators such as tertiaryamines and polyhydroxyl compounds, such as hexanetriol and glycerine,may be present during the hardening of the epoxidized acetals.

It has been found that in hardening the epoxide compounds of theinvention with carboxylic acid anhydrides, it is advantageous to useonly about 0.3 to 0.9 gram-equivalent of anhydride groups to 1gramequivalent of epoxide groups.

It has further been found that for some industrial applications, theproperties of the hardened epoxide acetals of the invention arefavorably influenced if they contain a certain proportion ofcorresponding acetals polycarboxylic acids such as phthalic acid, andalso aminopolyepoxides, such as those which are for example obtained bydehydrohalogenation of reaction products of epihalohydrins and primaryor secondary of which the epoxide groups have been wholly or par- 5amines such as n-butyl-amine, aniline or 4,4-ditially saponified tohydroxyl groups. Since the said cor- (m n m thylamin )-diphenyl methneresponding wholly or only partially hydrolyzed epox- The hardenableepoxide compounds or their mixides are generally formed simultaneously(b c u f tures with hardeners may have added thereto fillers, sidereactions) when the epoxidation is carried out in plasticisers coloringsubstances and the like at any accordance with the invention, it isgenerally advisable S age P i r to the hardening A p l bitumen, glassnot to isolate the pure diepoxides or polyepoxides from fi e mica.Powdered q Cellulose. kaolin, finely the reaction mixture. dividedsilica (aerosil) or metal powders can be used as The expression"hardening" as used herein means extenders and fillers. the conversionof the foregoing epoxide compounds to The mixtures of the epoxidecompounds of the ininsoluble and infusible resins. l vention and thehardeners can be used in the unfilled or The present invention furtherprovides hardenable filled condition, or in the form of solutions oremulmixtures which contain the epoxidized acetals of the insions, astextile auxiliaries, lamination resins, lacquers, vention together withhardening agents for epoxy coating agents, dipping resins, castingresins, brushing, resins, preferably dicarboxylic or polycarboxylic acidfilling and trowelling compounds, adhesives and the anhydrides. like orfor the production of such agents. The hardened The hardenable mixturesaccording to the invention epoxide compounds of the invention areespecially advantageously contain, as indicated above, a proporvaluableas insulating compounds for the electrical intion of the correspondingacetals of which the epoxide dustry. groups are wholly or partiallysaponified to hydroxyl The compounds of the general formulae I, II andIV groups and/or other polyhydroxyl compounds such as may also berepresented by following general formulae hexanetriol, which have across-linking action. Other la, lla and W0 without changing the scope ofthe invenpolyepoxides may be added to the hardenable epoxide tion:

(Rz)& R1

x4e: (Rl0) m J/ i R. 0

c (RA-)m-i Ru PJQ R1 R1 2')nl c In 0-011, c

R1C/ c cfi c c-Rr tlliolhu 0\ l/Ri 0- 011; 0 0- 'R1 113'" //R4' ,4 l(Rb-lei: n. m tRr'M-i Ila (RHQ (Ri' n-i io)2 m m'lr-n (mo; Flor-1compounds, e.g., monoglycidyl or polyglycidyl ethers of monoalcohols orpolyalcohols, (such as butyl alcohol, l,4-butanediol or glycerine) ofmonophenols or dehydes with phenols (novolaks), polyglycidyl esters of IVa In these fomulae m and n each represents a whole number of at themost 2, R,, R,, R,, R',, R R' R,. R',, R,,, R,, R,,, R,,, R,, R',, R,,,R',,, R and R, are of the group consisting of hydrogen atom, halogenatom, alkoxy group, aliphatic hydrocarbon radical, cycloaliphatichydrocarbon radical, araliphatic hydrocarbon radical and aromatichydrocarbon radical, preferably an alkyl group containing one to fourcarbon atoms, R and R each stands for an alkylene group, preferably fora methylene group, and A represents a tetravalent aliphatic radicalcontaining at least four carbon atoms and being free from any carbonatoms with more than a single free valency.

in the following examples, parts represent parts by weight, andpercentages represent percentages by weight; the ratio between parts byweight and parts by volume is the same as between kilograms and liters;the temperatures are given in degrees Centigrade.

EXAMPLE 1 Acetal of A -tetrahydrobenzaldehyde and l,l-bis-(hydroxymethyl)-cyclohex-3-ene Epoxide 1174 Parts of the acetaldescribed above are dissolved in 3000 parts by volume of benzene and 100parts of sodium acetate are added. 2200 Parts of 42 percent peraceticacid are added in portions during l 1% hours while stirring. Thetemperature is kept at about 30 by cooling. After the mixture hasreacted for another 2 hours at 30 while stirring constantly, it iscooled to Titration shows the consumption of the theoretical quantity ofperacetic acid.

The benzene solution is washed three times with 1000 parts by volume ofwater and l000 parts by volume of 2N sodium carbonate solution (the pHvalue of the aqueous solution should be about It) after extraction). Thecombined aqueous solutions are extracted with 1500 parts by volume ofbenzene. The combined benzene solutions are dried over sodium sulfate,filtered and concentrated by evaporation in vacuo. The last traces ofsolvent are removed under high vacuum at 100. There are obtained 1067parts of a crystal-clear, thickly liquid resin with an epoxide contentof 6.0 epoxide equivalents per kg.

For determining the epoxide content, about I g of epoxide is dissolvedin 30 ml of glacial acetic acid and titrated with 0.5 N hydrogen bromidein glacial acetic acid in the presence of crystal violet until the colorof the indicator changes to bluish-green. A consumption of 2 cc of 0.5NHBr-solution corresponds to one epoxide equivalent per kg.

EXAMPLE 2 Acetal from 6 methylA"-tetrahydrobenzaldehyde and I0 l,l-bis-(hydroxymethyl )-6-methyl-cyclohex-3-ene.

405 Parts of 6methyl-A -tetrahydrobenzaldehyde, 468 parts ofl,l-bis-(hydroxymethyl)-6-methylcyclohex-3-ene, 1 part oftoluene-p-sulfonic acid and [00 parts by volume of benzene are boiled ina cyclic distillation apparatus until the separation of water ceases.

There is then added to the solution 1 part of finely powdered anhydroussodium acetate and the solution is then filtered and concentrated byevaporation. The residue yields on distillation at ll8/0.3 mm.Hg 748parts of the condensation product.

Analysis: C H O,

calculated: C 77.82% H 9.99% O 12.20% found: C 77.63% H9.90% O [2.48%

Epoxide 473 Parts of the acetal described above are dissolved in 3000parts by volume of benzene. 30 Parts of anhydrous sodium acetate areadded and, over a period of l hour, 850 parts of 42 percent peraceticacid are added in portions and while stirring. The temperature is keptat 30 by external cooling. The mixture is stirred for another 4 hoursand kept at 30 by occasional cooling. Thereafter, it is left to standfor 14 hours at 0. Titration shows the consumption of the theoreticalquantity of peracetic acid.

The lower aqueous layer is separated. While cooling, 880 parts by volumeof concentrated sodium hydroxide solution are run into the thoroughlystirred benzene solution. The precipitated sodium acetate is filteredoff and the aqueous layer extracted with benzene. The combined benzenesolutions are concentrated by evaporation. There are obtained 487 partsof resin with an epoxide content of 5.2 epoxide equivalents per kg.

The epoxide can be distilled at approximately l08/0.07 mm.Hg.

Analysis: C I-[ 0 calculated: C 69.36% H 8.90% O 2l.74% found: C 69.42%H 8.87% O 22.01%.

EXAMPLE 3 Acetal from 2,5-endomethylene-A tetrahydrobenzaldehyde and l,1 -bis-( hydroxymethyl 6-methyl-cyclohex-3-ene.

A mixture of 122 parts of 2,5-endomethylene-A tetrahydrobenzaldehyde,156 parts of l,l-bis-(hydroxy-methyl)-6-methyl-cyclohex-3-ene, 0.5 partof toluene-p-sulfonic acid and 500 parts by volume of benzene is boiledin a cyclic distillation apparatus until the separation of water ceases.The mixture is neutralized with 1 part by volume of piperidine, thesolvent is evaporated and residue is distilled under high vacuum. Theproduct (202 parts) distils over at l35-l50/0.02 mm.Hg and immediatelysolidifies. For analysis purposes, a preparation is re-crystallized frommethanol;

Analysis: c,,i-|,,o,

calculated: C78.42% H9.29% found: C78.20% H9.38%.

Epoxide Parts of the acetal described above (crude product) aredissolved in 750 parts by volume of benzene. 30 Parts of sodium acetateare added and the acetal is epoxidized with 300 parts of 42 percentperacetic acid at 30 during I 1% hours. After this time, 95 percent ofthe theoretical amount of peracetic acid are consumed.

For working up, the benzene solution is washed with water and 2N sodiumcarbonate solution. After driving off the benzene, there are obtainedI58 parts of epoxide resin.

70 Parts of the epoxide resin obtained and 29 parts of phthalic acidanhydride are melted, mixed at about l25 and placed in an aluminumcasting mould. After hardening (7 hours at 120 and then 24 hours at160), the casting has the following properties:

Bending strength 7.81 kg/mm Impact bending strength 4.56 cmkg/cm Martensdimensional stability under heat EXAMPLE 4 Bis-( 6-methyl-A-tetrahydrobenzal )-D-sorbitol 95.6 Parts of D-sorbitol are condensed ina cyclic distillation apparatus with I35 parts of t'i-methyl-Atetrahydrobenzaldehyde in the presence of 0.5 part of toIuene-p-sulfonicacid and 500 parts by volume of .benzene. After boiling for 22 hours,the sorbitol is almost completely dissolved and the separation of waterceases. l g of finely powdered anhydrous sodium acetate is addedthereto, and the solution is then filtered and the filtrate isconcentrated by evaporation. There are obtained 161 parts of residue inthe form of a solid mass.

Bis-( 3,4-epxy-6-methyl-hexahydrobenzal )-D-sorbitol I52 Parts of thepreviously described bis-(6-methyl- A -tetrahydrobenzal)-D-sorbitol aredissolved in 750 parts by volume of benzene and parts of sodium acetateare added thereto. 200 Parts of 42 percent peracetic acid are addedduring minutes, while stirring and cooling. The mixture is kept foranother minutes at approximately 30 and after this time 96 percent ofthe theoretical amount of peracetic acid has been consumed.

The solution is washed three times with 250 parts of water and twicewith 250 parts of 2N sodium carbonate solution. The combined aqueoussolutions are extracted with 400 parts by volume of benzene. Thecombined benzene solutions, on being concentrated by evaporation, yield121 parts of resin with an epoxide content of 3.9 epoxide equivalentsper kg.

EXAMPLE 5 Bis-( o -tetrahydrobenzal )pentaerythritol 12 Analysis: C H Qcalculated: C 7l.22% H 8.81% O l9.97% found: C 7L5 l% H 8.73%0 19.96%

Bis-( 3 ,4-epoxyhexahydrobenzal )-pentaerythritol 960 Parts of thebis-(o -tetrahydrobenzal)-pentaerythritol (crude product) as describedabove are dissolved in 3000 parts by volume of benzene. I40 Parts ofanhydrous sodium acetate are added and then, over a period of l hour,I400 ports of 42 percent peracetic acid are added in portions and whilestirring. The temperature is kept at approximately 24-28 by colling.

benzene extraction of the aqueous solutions, it is possible to obtainsome further epoxide.

Parts of the epoxide resin which is obtained and 26 parts of phthalicacid anhydride are melted and mixed at about I2520 The mixture is placedin an aluminum casting mould and hardened for 7 hours at l20, and thenfor 24 hours at The casting has the following properties: Bendingstrength 0.39 kg/mm 2 Impact bending strength l0 l0 cmkg/cm Martenedimensional stability under rest EXAMPLE 6 Bis-(6-methyl-A-tetrahydrobenzal)-pentaerythritol A mixture of 248 parts of 6-methyI-Atetrahydrobenzaldehyde, I38 parts of pentaerythritol, 1 part oftoIuene-p-sulfonic acid and 500 parts by volume of benzene is boiled ina cyclic distillation apparatus until the separation of water ceases. 2Parts of anhydrous sodium acetate are added thereto and the solution isthen filtered and concentrated by evaporation. There are obtained 298parts of crystalline bis-(6- methyl-A -tetrahydrobenzal)-pentaenythritol.

Crystallization from methanol yields the product, m.p. I37-I42.

Analysis: C H O calculated: C 72.38% H 9.26% found: C 72.31% H 9.13%

Bis-( 3,4-epoxy-6-methyl-hexahyclrobenzal)- pentaerythritol 298 Parts ofthe previously described bis-(6-methyl- A-tetrahydro-benzal)-pentaerythritol (crude product) are dissolved in1200 parts by volume of benzene. 35 Parts of anhydrous sodium acetateare added and then, over a period of I hours, 500 parts of 42 percentperacetic acid are added while stirring. The temperature is kept at 30by cooling. The mixture is allowed to react for another 2 hours at 2527.The aqueous phase is separated and the benzene layer is washed threetimes with 300 parts of water and twice with 250 parts of sodiumcarbonate solution. The aqueous parts are extracted with 400 parts byvolume of benzene. The combined benzene solutions are dried over sodiumsulfate, filtered and concentrated by evaporation. There are obtained285 parts of solid resin with an epoxide content of 3.9 epoxideequivalents per kg.

65 Parts of the epoxide resin which is obtained are mixed with parts ofphthalic acid anhydride, melted and placed in an aluminum casting mould.The casting is hardened for 7 hours at 120 and then for 24 hours at 160.it has the following properties:

Bending strength 10.14kg/mm lmpact bending strength 7.24cmkg/cm EXAMPLE7 Tris-( A tetrahydrobenzal )-D-mannito1 182 Parts of D-Mannitol aresuspended in 1000 parts by volume of benzene and 2 parts oftoluene-p-sulfonic acid are added thereto. The suspension is heatedwhile stirring in a cyclic distillation apparatus to boiling point and354 parts of A -tetrahydrobenzaldehyde are added thereto. After 8 hours,1 part of toluene-p-sulfonic acid and 46 parts of d-tetrahydrobenzaldehyde are introduced. The mixture is boiled foranother 14 hours, 6 parts of anhydrous sodium acetate are then added,and the product is filtered and concentrated by evaporation. There arethus obtained 474 parts of solid noncrystalline residue.

Tris-( 3,4-epoxyhexahydrobenza1)-D-mannito1 200 Parts of the tris-(A-tetrahydrobenzaD-D-mannitol previously described are dissolved in 1000parts by volume of benzene and 20 parts of anhydrous sodium acetate areadded thereto. During 40 minutes, while constantly stirring and cooling(internal temperature 300 parts of 42 percent per-acetic acid are addedin portions. The mixture is stirred for another 2 hours and kept at 30.It is then cooled with ice and the benzene solution is washed with waterand 2N sodium carbonate solution until neutral in reaction. Afterevaporating the benzene, there are obtained 208 parts of resin with anepoxide content of 5.4 epoxide equivalents per kg. 60 Parts of theepoxide resin which is obtained and 33 parts of phthalic acid anhydrideare melted and homogeneously mixed at 130. The mixture is introducedinto an aluminum casting mould and hardened for 1 hour at 120 and thenfor 15 hours at 150. The casting has the following properties:

Bending strength 7.4 kg/mm lmpact bending strength 4.0 cmkg/cm Waterabsorption after 4 days at room temperature 0.69% Martens dimensionalstability EXAMPLE 8 Bis-( d -tetrahydrobenzal )-glucose 90 Parts ofanhydrous glucose, 120 parts of A tetrahydrobenzaldehyde, 0.5 part oftoluene-p-sulfonic acid and 500 parts by volume of benzene are boiled ina cyclic distillation apparatus while stirring. After heating for about50 hours, the separation of water ceases. There is then added to thesolution 1 part of anhydrous sodium acetate and the solution is thenfiltered and concentrated by evaporation. There are obtained 160 14parts of crude bis-( A -tetrahydrobenzal )-glucose.

Epoxide 160 Parts of the acetal described above are dissolved in 500parts by volume of benzene. 20 Parts of sodium acetate are added to thesolution and during 42 minutes, 200 parts of 42 percent peracetic acidare introduced at 30, while stirring and cooling. The mixture is keptfor another 50 minutes at 30 and then cooled to 0. The organic phase iswashed three times with 200 parts of water and twice with 200 parts ofsodium carbonate solution. The combined aqueous solutions are extractedwith 300 pans by volume of benzene. On concentrating the combinedbenzene solutions by evaporation, there are obtained 143 parts of solidepoxide resin with an epoxide content of 4.7 epoxide equivalents per kg.

EXAM PLE 9 150 Parts of the commercial first-hydrolysis compound whichis formed when cellulose is obtained from wood (first-fraction sugar)and which contains 76.5 percent of dry substance, are boiled whilestirring in a cyclic distillation apparatus with 220 parts of A"-tetrahydrobenzaldehyde in the presence of 400 parts by volume of benzeneand 2 parts of toluene-p-sulfonic acid. After 36 hours 50 parts of waterare separated. On standing at room temperature, a crystalline materialis precipitated. The mixture is ,filtered and concentrated byevaporation. The residue is dissolved in 1500 parts by volume ofchlorobenzene. 390 Parts of 33 percent peracetic acid (free fromsulfuric acid) are added in portions to the thoroughly stirred solution.The temperature is kept at 27-33 by cooling. After 1 A hours, 78 partsof peracetic acid (calculated at 100 percent) are consumed. The organicphase is separated and concentrated by evaporation under water-pumpvacuum. There are thus obtained 127 parts of a solid slightlycoloredresin with an epoxide content of 3.7 epoxide equivalents per kg.

EXAMPLE I0 440 Parts of A tetrahydrobenzaldehyde (4 mols) are mixed with352 parts of 2,3-buten-1,4-dio1. Heat is developed, the temperaturerising from 20 to 42. After 30 minutes, the mixture is cooled and 1.5parts by volume of 50 percent sulfuric acid and 1500 parts by volume ofbenzene are added. The mixture is then heated to boiling point and thewater formed in the reaction is distilled off azeotropically. Theseparation of the water parts) takes 1 10 minutes. The benzene is thendistilled off under partial vacuum, 10 parts of anhydrous sodium acetateare added and the reaction mixture is subjected to fractionaldistillation at 11 mrn.Hg. The following fractions are obtained:

45-55 37 parts of A -tetrahydrobenzaldehyde 121 564 parts ofacetalResidue 199 parts (contains butendiol Epoxide 54 Parts of the previouslydescribed acetal are dissolved in 200 parts of benzene and 6 parts ofanhydrous sodium acetate are added. 121 Parts of 39.6 percent peraceticacid are then added dropwise over a period of 15 minutes. By gentlecooling, the temperature is kept EXAMPLE I 1 I Parts of butadienemonoxide are mixed with 400 parts by volume of carbon tetrachloride andwith 220 parts of A -tetrahydrobenzaldehyde. 20 Parts of tintetrachloride, dissolved in 100 parts by volume of carbon tetrachloride,are then added dropwise over a period of 45 minutes. The temperature iskept at 39"42 by cooling. Thereafter, the mixture is left for another 2hours at the same temperature. It is then cooled and run into 500 partsby volume of substantially 20 percent sodium hydroxide solution. Theorganic phase is separated, dried with sodium sulfate, tiltered andconcentrated by evaporation. By distillation of the residue, there areobtained at l05-l27 mm, 101 parts of crude acetal. Further distillation,through a Raschig column of height 30 cm, yields a product b.p. ll7-ll8/l8mm.

Analysis: C I-L 0,

calculated: C 73.30 percent H 8.95% found: C 72.9% H 9.0%.

18.0 Parts of the cyclic acetal are mixed with 500 parts by volume of achloroform solution of 34.8 parts of perbenzoic acid. By gentle cooling,the temperature is kept at 20-25. Half of the theoretical quantity ofperbenzoic acid is consumed after about half an hour and the completeepoxidation takes 2 5: days. The chloroform solution is shaken withsodium carbonate solution, dried, filtered and concentrated byevaporation, a thickly liquid epoxide being obtained.

EXAMPLE I2 193 Parts of dicyclopentadiene are dissolved in I000 parts byvolume of benzene. in the presence of 35 parts of sodium acetate, thesolution is allowed to react with 300 parts of 42 percent peracetic acidat 30-32 until 60 percent of the quantity of peracetic acid necessaryfor epoxidation of both double bonds is consumed. The benzene solutionis washed free from acid with water and sodium carbonate solution andthen evaporated.

I50 Parts of the residue which is obtained and I I0 parts of A-tetrahydrobenzaldehyde are dissolved in 1000 parts by volume of carbontetrachloride. A mixture of 20 tin of time tetrachloride and 50 parts byvolume of carbon tetrachloride are added dropwise to the solution at30-40 within 1 hour. After the mixture has stood for one day at roomtemperature, it is shaken with 500 parts by volume of substantially 20percent sodium hydroxide solution. The organic phase is separated, driedover sodium sulfate and concentrated in vacuo, 234 parts of residuebeing obtained.

200 Parts of the product which is obtained are allowed to react inbenzene solution in the presence of 35 parts of sodium acetate with 350parts of 42 percent peracetic acid at 29-32. After l 1% hours, ll8 parts(calculated as percent) of peracetic acid are consumed. The solution iswashed free from acid with water and sodium carbonate solution dried andevaporated. I46 Parts of solid epoxide are obtained.

EXAMPLE 13 Samples of a cycloaliphatic polyepoxide (Resin A) preparedaccording to Example I and also a polyglycidyl ether resin which isliquid at room temperature and which has an epoxide content of about 5.3epoxide equivalents per kg, prepared by reacting epichlorhydrin withbis-(4-hydroxyphenyl)-dimethyl methane in the presence of alkali (ResinC) and samples of mixtures of resins A and C in two difi'erent ratios,are melted with phthalic acid anhydride as hardening agent at l20-l30,0.75 equivalent of anhydride groups being used in each case to oneequivalent of epoxide groups of the resins A and C and of the resinmixtures.

The mixtures are all cast in aluminum moulds (40 X 10 X I40 mm) at aboutand hardened for 24 hours at The dimensional stability under heat of thehardened cast samples is shown in the following Table:

Parts Resin A Parts Resin C Dimensional stability under heat accordingto Martens (DIN) C.

EXAMPLE 14 Samples of a cycloaliphatic polyepoxide compound (Resin B)prepared according to Example 2, and also a cycloaliphatic epoxide esterof the fonnula:

CHzH-CO 0 0 CH; CH;

Martens dimensional stability under heat Equivalent phthalic acidanhydride per 1 equivalent epoxide (DIN) in C with groups Resin 8 ResinD 045 I84 7| 085 I84 163 090 I67 I49 EXAMPLE 15 28.5 Parts of phthalicacid anhydride are dissolved at l20l30 in I parts of the cycloaliphaticepoxide resin A prepared according to Example I. The mixture has aviscosity of less than 20 centipoises at 120 and a viscosity of I500centipoises after 1 r hours at 120.

A first portion of the mixture is cast in an aluminum mould (40 X X I40mm) and is hardened, initially for 24 hours at 140 and then for 24 hoursat 200. The casting which is obtained has an exceptionally highdimensional stability (measured according to Martens DIN) of 230.

A second portion of the above mixture is cast on to glass plates inthicknesses of [H0 mm and I mm and hardened for 24 hours at I40". Theresulting films are resistant to treatment for I hour at roomtemperature with 5N-sulfuric acid, SN-sodium hydroxide solution, water,acetone and chlorobenzene.

EXAMPLE I6 I00 Parts of a cycloaliphatic polyepoxide resin prepared in amanner analogous to Example I and having an epoxide content of 7.0epoxide equivalents per kg are mixed at room temperature with 7.9 parts(Sample 1 and with [5.9 parts (Sample 2) of 2,4-dihydroxy-3-oxymethyl-pentane. As hardening agent, there are used in both cases 31parts of phthalic acid anhydride (0.3 equivalent of anhydride groups per1 epoxide group).

The phthalic acid anhydride is dissolved as described in Example 15. Themixtures are cast in aluminum moulds as in Example I3 and hardened for24 hours at 140. The hardened castings have the following proper ties:

Sample Impact bending strength Dimensional stability under heataccording to Martens (DIN) in C EXAMPLE 17 perature in each case. Thecasting mixtures thus obtained are cast at room temperature and bothinitially hardened for 16 hours at I00 and then for 24 hours at I60. Thebending strength and the dimensional stability under heat ofthe hardenedcastings are compared below:

Sample Bending strength Martens dimensional stability ltg/mm under heat(DIN) in "C I I0.2 I53 2 9t I36 mixtures being liquid at roomtemperature.

EXAMPLE I8 I00 Parts of the cycloaliphatic epoxide resin B preparedaccording to Example 2, are mixed at room temperature with 24.5 parts oftriethylene tetramine as hardening agent.

A first part of the hardenable mixture is cast, as described in Example17, in 21 aluminum mould at room temperature, while a second portion ofthis mixture is used for the production of adhesive joints. For thelatter purpose, degreased and polished aluminum sheets (I X 25 X 15overlap I0 mm) are stuck together, the said sheets being obtainableunder the name Anticorodal B".

The hardening in each case is carried out initially for I7 hours at 200and then for 24 hours at I60". The properties of the hardened castingsand the adhesive joints are as follows:

Bending strength 1 L0 kg/mm Dimensional stability under heat accordingto Martens(DlN) lIl Tensile-shear strength What is claimed is:

The diepoxy compound having the formula I.2 ltg/mm 2 3 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,9 9 D t d August 8,1972 Inventor(s) HANS BATZER ET AL It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Cover page, after "Ciba-Geigy AG" insert Basle,

Switzerland Signed and sealed this 30th da of April 197M.

(SEAL) AttOSti EDIJARD I IJ LETGILEEI TR. C. MARSHALL DANN Atte sting;Officer Commissioner of Patents

-. The diepoxy compound having the formula